Polymers prepared from 4,4&#39;-bis(2-(amino(halo) phenoxyphenyl) hexafluoroisopropyl) diphenyl ether

ABSTRACT

This invention relates to new fluorine-containing polyimides, polyamide-acids/esters, polyamides, addition polyimides and imide oligomers which exhibit low melting points, better solubilities, low dielectric constants, superior thermal and thermal oxidative stability, and improved processing characteristics. 
     The product of this invention are characterized by the fact that they are derived from 4,4&#39;-bis[2-(amino(halo)phenoxyphenyl)-hexafluoroisopropyl]diphenyl ether.

FIELD OF THE INVENTION

This invention relates to new fluorine-containing polyimides,polyamide-acids/esters, polyamides, addition polyimides and imideoligomers which exhibit low melting points, better solubilities, lowdielectric constants, superior thermal and thermal oxidative stability,and improved processing characteristics.

BACKGROUND OF THE INVENTION

Polyimides are widely used in the aerospace industry and electronicsindustry, because of their toughness, low density, thermal stability,radiation resistance and mechanical strength. However, it is recognizedthat polyimides are difficult to process. The processing problems arisefrom the insolubility of polyimides in most of the more common solvents.Consequently, products were fabricated from polyamide-acidintermediates, which are more soluble but less stable, and then imidizedto provide the desired end product. The disadvantage of this process isthat the water liberated during the imidization of the polyamide-acidforms undesirable voids or surface irregularities in the final productwhich reduce its mechanical properties.

Another approach is to provide a fully imidized prepolymer havingreactive end groups. In this way, the water formed during imidization isremoved before the final cure of the prepolymer. The resulting polyimideproduct is typically a thermoset plastic. However, the imidizedprepolymers are not as soluble as would be desired.

It has been suggested that polyimides having a singlehexafluoroisopropylidene linking group in the diamine or dianhydridecomonomers have improved solubility properties. Several patents disclosepolyimides prepared from diamines of this type. For example, U.S. Pat.No. 3,356,648 to Rogers discloses polyimides prepared from2,2-bis(4-aminophenyl) hexafluoropropane; U.S. Pat. No. 4,592,925 toDuPont et al. discloses polyimides prepare from 2,2-bis(3-aminophenyl)hexafluoropropane; U.S. Pat. No. 4,111,906 to Jones et al. disclosespolyimides prepared from 2,2-bis[4(4-aminophenoxy)phenyl]hexafluoropropane; and U.S. Pat. No. 4,477,648 to Jones et al. disclosespolyimides prepared from 2,2-bis[(2-halo4-aminophenoxy)phenyl]hexafluoropropane.

SUMMARY OF THE INVENTION

The present invention seeks to provide polyimides and polyamides havingimproved solubility and processing characteristics by incorporating intothe polymeric chain a novel aromatic diamine compound having twohexafluoroisopropylidene linking groups. The diamine may becharacterized by the general formula: ##STR1## wherein X is hydrogen orhalogen. The preferred diamine is4,4'-bis[4-aminophenoxyphenyl)hexafluoroisopropyl] diphenyl ether. Thepolyimides are prepared by reacting these diamines with tetracarboxylicacids or derivatives thereof. The polyamides are prepared by reactingthe diamines with the acid chlorides of dicarboxylic acids. It has beenfound that the polyimides of this invention also have low dielectricconstants.

In another aspect, the invention also provides new monomers, oligomersand their corresponding addition polyimides. The monomers and oligomersare formed by reacting the new diamines with dianhydrides and reactiveend-capping compounds such as aromatic ethynyl amines, nadic anhydrides,benzocyclobutenes, or maleic anhydrides. The resulting imide monomersand oligomers may then be cured by addition reactions.

In yet another aspect, the invention provides polymer precursorcompositions, epoxy resin hardeners, matrix resins, composites,laminates, films, fibers, adhesives, coatings, photoresists and moldedarticles.

DETAILED DESCRIPTION OF THE INVENTION

The polyimides of this invention may be characterized as havingrecurring groups of the structure: ##STR2## wherein n is the number ofrepeating groups, R is a tetravalent organic radical having at least 4carbon atoms, Q is ##STR3## and X is hydrogen or halogen, preferablyhydrogen.

Preferably Q is ##STR4##

These polyimides are prepared by reacting tetracarboxylic acids orderivatives thereof such as esters or dianhydrides and a diamine of theformula: ##STR5## When the amino group is in the meta position on thephenyl ring in relation to the ether linking group, X is hydrogen. Whenthe amino group is in the para position, X may be hydrogen or halogen.The preferred halogen is chlorine. The preferred diamine is ##STR6##

EXAMPLE 1 Preparation of 4,4'-bis[2-(4-Aminophenoxyphenyl)Hexafluoroisopropyl] Diphenyl Ether

4,4'-bis[2-(4-hydroxyphenyl)hexafluoroisopropyl] diphenyl ether isprepared by charging a stainless steel pressure vessel with4,4'-bis(2-hydroxy-hexafluoroisopropyl) diphenyl ether, phenol andhydrogen fluoride in a molar ratio of at least 1:2:10 and heating totemperatures of between 100 to 170° C. for 24 to 96 hours whilestirring. After removing hydrogen fluoride by evaporation, the solidresidue is dissolved in ethanol and purified by refluxing in thepresence of charcoal. From the filtered solution, a white crystallineprecipitate is obtained having a melting point of 179°-180° C.

A 2,000 ml round bottom flask equipped with stirrer, thermometer,condensor, and a nitrogen blanket is charged with 765 ml of dimethylsulfoxide and 200 g of 4,4'-bis[2-(4-hydroxyphenyl) hexafluoroisopropyl]diphenyl ether. The mixture is dissolved at room temperature resultingin a brown solution. Over a five minute period, 39.75 g of sodiummethoxide anhydrous powder is added to form a disodium salt. The mixtureis stirred for about one hour without temperature control. A solution of106 g of 1-chloro-4-nitrobenzene in 250 ml of dimethyl sulfoxide isadded over a period of about one half hour. The reaction mixture isheated to 100° C. and maintained at this temperature for about 20 hoursand then allowed to cool. The reaction solution is then transferred to a4 liter beaker. While stirring, 600 ml of methanol is dropwise added tothe solution followed by the dropwise addition of 250 ml of distilledwater to promote crystallization. The crystallized precipitate isfiltered, washed with distilled water, and dried overnight in a vacuumoven at 60° C. The yield is 315 g of partially dried crude4,4'-bis[2-(4-nitrophenyl)-hexafluoroisopropyl] diphenyl ether.

A 2000 ml erlenmeyer flask is charged with the 315 g of the crudereaction product and 410 ml of acetone. The mixture is heated todissolve the crude product and then clarified. 700 ml of isopropanol isadded to the hot solution. The solution is cooled to 10° C. and theprecipitate is filtered and washed with isopropanol. The yield is 190.6g of the dinitro compound when dried.

A 500 ml PARR bottle is charged with 300 ml of ethyl acetate, 86 g ofthe dinitro compound and 5 g of 3% Pd/carbon catalyst. The bottle ispurged with nitrogen and then placed in a hydrogenation apparatus. Thebottle is then purged twice with hydrogen. Under agitation, the reactionmixture is heated to and maintained at about 70° C. and maintained underabout 70 psi of hydrogen for about one and a half hours when hydrogenuptake is stopped. It is then allowed to cool to room temperature. Thecatalyst is filtered off and washed with 20 ml of ethyl acetate. Theethyl acetate is then evaporated leaving 92.5 g of a crude syrup. Thesyrup is dissolved in 175 ml of isopropanol. 15 g of 32% HCl is dropwiseadded to the solution to form the amine hydrochloride. The mixture iscooled to 10° C. and the precipitate is filtered, washed with 50 ml ofisopropanol, and dried. The amine hydrochloride is then reslurried in3000 ml of distilled water and the pH is adjusted to 11 with about 5 gof 50% sodium hydroxide. While maintaining the pH at 11, the slurry isstirred overnight to form the free diamine. The diamine is filtered off,washed with 100 ml of distilled water, and dried in a vacuum oven. Theyield is 73.8 g of dry4,4'-bis[2-(4-aminophenoxyphenyl)hexafluoroisopropyl] diphenyl ether(about 90 percent yield from the dinitro compound).

A diamine wherein X is halogen may be obtained by substituting a molarequivalent amount of a 3,4-dihalonitrobenzene such as 129.2 g of3,4-dichloronitrobenzene for the 1-chloro-4-nitrobenzene in the aboveprocedure.

The diamines of formula (4) may be reacted with tetracarboxylic acids oresters having a formula: ##STR7## or with dianhydrides having theformula: ##STR8## wherein R is a tetravalent organic radical having atleast 4 carbon atoms and R₁ is hydrogen or a monavalent organic radical.Preferably R comprises an aromatic moiety such as a phenylene ornaphthalene group which may comprise substituent halogen, hydroxy, lower(C₁ -C₆) alkyl or lower (C₁ -C₆) alkoxy groups. Preferably R is selectedfrom the group consisting of ##STR9## wherein R₂ is a carbon-carbonbond, --O--, --S--, --SO₂ --, --CO--, --(CH₂)_(r) --, ##STR10## whereinR₃ is a carbon-carbon bond, --S--, --SO₂ --, --CO--, --CH₂ --, --C₂ H₄--, ##STR11## R₄ is halogen, hydroxy, lower (C₁ -C₆) alkyl or lower (C₁-C₆) alkoxy, m is 0 to 2, preferably m is 0, r is 1 to 4, and s is 1 to5.

Illustrative of tetracarboxylic acid dianhydrides which are suitable foruse in the present invention are:

1,2,4,5-benzene tetracarboxylic acid dianhydride;

1,2,3,4-benzene tetracarboxylic acid dianhydride;

1,4-bis(2,3-dicarboxyphenoxy) benzene dianhydride;

1,3-bis(3,4-dicarboxyphenoxy) benzene dianhydride;

1,2,4,5-naphthalene tetracarboxylic acid dianhydride;

1,2,5,6-naphthalene tetracarboxylic acid dianhydride;

1,4,5,8-naphthalene tetracarboxylic acid dianhydride;

2,3,6,7-naphthalene tetracarboxylic acid dianhydride;

2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride;

2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride;

2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride;

3,3',4,4'-diphenyl tetracarboxylic acid dianhydride;

2,2',3,3'-diphenyl tetracarboxylic acid dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride;

bis(2,3-dicarboxyphenyl) ether dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy) diphenyl ether dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) diphenyl ether dianhydride;

bis(3,4-dicarboxyphenyl) sulfide dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride;

bis(3,4-dicarboxyphenyl) sulfone dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy) diphenyl sulfone dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride;

3,3',4,4'-benzophenone tetracarboxylic acid dianhydride;

2,2',3,3'-benzophenone tetracarboxylic acid dianhydride;

2,3,3',4'-benzophenone tetracarboxylic acid dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride;

bis(2,3-dicarboxyphenyl)methane dianhydride;

bis(3,4-dicarboxyphenyl)methane dianhydride;

1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride;

1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride;

1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride;

2,2-bis(2,3-dicarboxyphenyl)propane dianhydride;

2,2-bis(3,4-dicarboxyphenyl)propane dianhydride;

2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;

4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propanedianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy-3,5-dimethyl)phenyl]propane dianhydride;

1,2,3,4-butane tetracarboxylic acid dianhydride;

1,2,3,4-cyclopentane tetracarboxylic acid dianhydride;

2,3,4,5-thiophene tetracarboxylic acid dianhydride;

2,3,4,5-pyrrolidine tetracarboxylic acid dianhydride;

2,3,5,6-pyrazine tetracarboxylic acid dianhydride;

1,8,9,10-phenanthrene tetracarboxylic acid dianhydride;

3,4,9,10-perylene tetracarboxylic acid dianhydride;

2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride;

1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;

1,1-bis(3,4-dicarboxyphenyl)-1-phenyl-2,2,2-trifluoroethane dianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride;

1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethanedianhydride;

and mixtures thereof.

A mixture of at least two suitable tetracarboxylic acids or derivativesthereof may be reacted with a diamine of formula (4) to producecopolyimides.

One skilled in the art will recognize that the tetracarboxylic acids andacid-esters of the above-listed dianhydride compounds may also be usedto produce the polyimides. These tetracarboxylic acids or derivativesthereof are available or may be prepared by known methods. For example,U.S. Pat. No. 3,847,867 to Heath et al. and U.S. Pat. No. 4,650,850 toHowson, which are incorporated herein by reference, show the preparationof bis(ether anhydrides)) and bis(dialkyl aromatic ether anhydrides)),respectively. The preparation of fluorine-containing dianhydrides isdisclosed in U.S. Pat. No. 3,310,573 to Gordon and U.S. Pat. No.3,649,601 to Critchley et al., which are also incorporated herein byreference.

Preferred polyimides are those prepared from the diamine of formula (5)and dianhydrides of the formula: ##STR12##

The 12F-DA dianhydride may be prepared in the following manner:

EXAMPLE 2 Preparation of 4,4'-bis[2-(3,4-Dicarboxyphenyl)Hexafluoroisopropyl] Diphenyl Ether Dianhydride

To a stainless steel reactor 4,4'-bis(2-hydroxyhexafluoroisopropyl)diphenyl ether, o-xylene and hydrogen fluoride are charged in a molarratio of at least 1:2:10. The reaction mixture is stirred in the closedreactor under autogenous pressure at temperatures of between 100° and170° C. for 24 to 96 hours. After evaporation of the hydrogen fluorideat 80° C., the contents of the reactor are poured into ice. The formedorganic layer is separated, diluted with methylene chloride, and driedover calcium chloride. After evaporation of the solvent, the crudeproduct is treated with charcoal in chloroform, filtered andrecrystallized. The 4,4'-bis[2-(3,4-dimethylphenyl)hexafluoroisopropyl]-diphenyl ether has a melting point 139°-141° C. Thethusly obtained diphenyl ether is dissolved in acetic acid and chargedin to a glass pressure vessel. A catalytic amount of a solution ofCo(OAc)₂ ·4H₂ O, Mn(OAc)₂ ·4H₂ O, HBr and acetic acid is added. Thereaction mixture is heated up to 180° C. under an oxygen pressure of 7.5bar. The exothermic reaction starts at about 90° C. with oxygen uptakeand is finished in 2 hours at 180° C. The reaction product is thentreated with a small amount of oxalic acid dihydrate in acetic acid.After heating the mixture to reflux temperature for 2 hours, thesolution is filtered. Acetic acid and water are distilled off. Aceticacid anhydride is added to the residue and the solution is heated to120° C. for one hour. After cooling to room temperature, the crystallineproduct is isolated, washed three times with a mixture of acetic acidand its anhydride, and dried in vacuo yielding4,4'-bis[2-(3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl etherdianhydride. M.P. 168°-170° C.

A preferred process for preparing the polyimides of this inventioninvolves first preparing a polyamide-acid by reacting the diamine andthe tetracarboxylic acid or derivative such as the dianhydride in anorganic solvent, preferably under substantially anhydrous conditions fora time and at a temperature sufficient to provide at least 50% of thecorresponding polyamide-acid, and then converting the polyamide-acid tothe polyimide. Suitable conditions for reacting the diamine and thedianhydride are disclosed in detail in U.S. Pat. Nos. 3,356,648 and3,959,350, both to Rogers, which are incorporated herein by reference.The intermediate polyamide-acid may also be esterified to providepolyamide-esters.

The polyamide-acids/esters are characterized by the formula: ##STR13##wherein n is the number of repeating groups, R is a tetravalent organicradical as defined above, R' is hydrogen or a monovalent organicradical, and Q is a divalent radical as defined in formula (2).Preferably, Q has the structure of formula (3). In addition to beinguseful to produce polyimides, the polyamide-acids may be esterified withthermally polymerigable or photopolymerizable compounds such asolefinically unsaturated monoepoxides to produce polyamide-esters usefulin photoresist compositions.

The polyamide-acids/esters may be cyclicized to form polyimides.Conversion to the polyimides may be accomplished by a heat treatment, achemical treatment or both as described in the above-referenced Rogerspatents.

In a preferred process for preparing the polyimides, the diamine anddianhydride are reacted in gamma-butyrolactone (BLO), or a mixture ofBLO and another solvent such as diglyme. The resulting product is apolyamide-acid which is then converted to the desired polyimide by oneof several methods: heating the polyamide-acid solution untilimidization is substantially complete; or by combining thepolyamide-acid solution and a dehydrating agent, with or withoutcatalyst, and optionally heating the resulting mixture until imidizationis substantially complete. The use of the BLO solvent provides severaladvantages in that it avoids the formation of complexes of thepolyamide-acid and the solvent that typically occur when solvents suchas N-methyl pyrrolidone (NMP) are used and allows the removal of thesolvent to proceed at lower temperatures (below 250° C.) to obtain asubstantially uniform films. When mixed with diglyme, the ratio byvolume of BLO to diglyme is preferably in the range of about 10:90 to90:10, more preferably of about 40:60 to 60:40.

The following examples are illustrative of the invention:

EXAMPLE 3

To a 250 ml reaction unit fitted with a condenser, thermometer, stirrerand nitrogen blanket, and purged with nitrogen, 16.72 g (0.02 moles) of4,4'bis[2-(4-amino-phenoxyphenyl)hexafluoroisopropyl]diphenyl ether(hereinafter "12F-ODA") are charged along with 50 g of distilledN-methyl pyrrolidone (NMP) under nitrogen atmosphere. The mixture isstirred to get a clear solution. To the clear, very pale yellow colorsolution, 15.24 g (0.02 moles) of 4,4'-bis[2(3,4-dicarboxyphenyl)hexafluoroisopropyl]diphenyl ether dianhydride (hereinafter "12F-DA")are charged while stirring is continued. 78 g of NMP is added to thereaction mixture which is then stirred overnight at room temperature.The resulting polyamic acid has an inherent viscosity of 0.60 dl/g,measured at 0.5 g/dl at 25° C. in dimethyl acetamide (DMAc). 36.00 g ofacetic anhydride and 3.60 g of 3-picoline are added to 140 g of thepolyamic acid solution. The reaction is stirred at room temperature forabout six hours and the resulting polyimide is precipitated in methanol,isolated by filtration, washed with fresh methanol, and dried overnightin a vacuum over at 85° C. It is soluble in acetone, DMAc, diglyme, MEK,NMP, THF, chloroform, BLO solvents.

A film is prepared from a solution comprising 20% by weight solids in a50/50 mixture by volumen of BLO/diglyme and cured to 350° C. by stepwiseheating. A very pale yellow, clear, flexible, self-supporting, toughfilm is obtained. Its glass transition temperature (T_(g)) is 222° C. bydifferential scanning calorimetry (DSC) and 5% weight loss is at 527° C.by thermal gravimetric analysis (TGA). Tensile strength is about 11800psi at room temperature. Tensile modulus is about 284 Ksi at roomtemperature, elongation at break is about 9% at room temperature, and ithas a limiting oxygen index of 46. The dielectric constant, measured ona Hewlett Packard Automated Newword Analyzer at ambient temperature overa frequency range of 8-12 GHz, is 2.45.

EXAMPLE 4

To a 250 ml reaction unit fitted with a condenser thermometer, stirrerand nitrogen blanket, and purged with nitrogen, 12.54 g (0.015 moles) of4,4'bis[2-(4-aminophenoxyphenyl)hexafluoroisopropyl] diphenyl ether(hereinafter "12F-ODA") are charged along with 40 g of distilledN-methyl pyrrolidone (NMP) under nitrogen atmosphere. The mixture isstirred to get a clear solution. To the solution, 6.66 g (0.015 moles)of 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride(hereinafter "6F-DA") are charged while stirring is continued. 36.8 g ofNMP are added to the reaction mixture which is then stirred overnight atroom temperature. The resulting polyamic acid has an inherent viscosityof 0.62 dl/g, measured at 0.5 g/dl at 25° C. dimethyl acetamide (DMAc).22 g of acetic anhydride and 2.2 g of 3-picoline are added to 85 g ofthe polyamic acid solution. The reaction is stirred at room temperaturefor about six hours and the resulting polyimide is precipitated inmethanol, isolated by filtration, washed with fresh methanol, and driedovernight in a vacuum over at 85° C. It is soluble in acetone, DMAc,diglyme, MEK, NMP, THF, chloroform, BLO solvents.

A film is prepared from a solution comprising 15% by weight solids in a50/50 mixture by volume of BLO/diglyme and cured to 350° C. by stepwiseheating. A very pale yellow, clear, flexible, self-supporting, touchfilm is obtained. Its glass transition temperature (T_(g)) is 226° C. bydifferential scanning calorimetry (DSC) and 5% weight loss is at 525° C.by thermal gravimetric analysis (TGA). Tensile strength is about 11100psi at room temperature. Tensile modulus is about 296 Ksi at roomtemperature, elongation at break is about 11% at room temperature, andit has a limiting oxygen index of 46. The dielectric constant, measuredon a Hewlett Packard Automated Network Analyzer at ambient temperatureover a frequency range of 18-12 GHz, is 2.46.

EXAMPLES 5-8

Polyimides are prepared in accordance with the procedure set forth inExample 3 by reacting the 12F-ODA diamine with the followingdianhydrides:

1,2,4,5-benzene tetracarboxylic acid dianhydride(PMDA),

3,3',4,4'-diphenyl tetracarboxylic acid dianhydride (BPDA),

3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA),

and bis(3,4-dicarboxyphenyl) ether dianhydride (ODPA).

The properties of the resulting polyimides are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                      Example Number                                                                5    6    7    8                                            Dianhydride       PMDA BPDA BTDA ODPA                                         __________________________________________________________________________             Units                                                                Ratio of millimole/                                                                             20/20                                                                              20/20                                                                              20/20                                                                              15/15                                        12F-ODA/ millimole                                                            Dianhydride                                                                   Inherent dl/g at  0.93 0.77 0.72 0.88                                         Viscosity                                                                              25° C. in DMAc                                                (Polyamic Acid)                                                               Inherent dl/g at  --   0.66 0.62 0.71                                         Viscosity                                                                              25° C. in DMAc                                                (Polyimide)                                                                   Glass Transi-                                                                          °C.                                                                             260  240  227  242                                          tion Temp. (Tg)                                                               5% Weight loss                                                                         °C.                                                                             520  520  530  520                                          in air (TGA)                                                                  Tensile Strength                                                                       psi      7,800                                                                              15,500                                                                             11,800                                                                             12,000                                       at room temp.                                                                 Tensile Modulus                                                                        Ksi      240  330  350  330                                          at room temp.                                                                 Elongation at                                                                          %        15.2 9.8  6.5  7.7                                          break                                                                         __________________________________________________________________________

The polyimides exhibit good solubility properties in solvents such asN-methyl pyrrolidone (NMP), dimethyl acetamide (DMAc), diglyme,methylethylketone (MEK), tetrahydrofuran (THF), acetone, chloroform,butyrolactone (BLO), dimethylsulfoxide (DMS), dimethylformamide (DMF)and the like.

The polyimides of this invention may be molded using standard techniquessuch as compression molding or injection molding to produce meltfabricated articles such as safety maskes, windshields, electroniccircuit substrates, airplane windows or the like. They may be compoundedwith graphite, graphite fiber, molybdenum disulphide or PTFE for theproduction of self-lubricating wear surfaces useful for piston rings,valve seats, bearings and seals. They may also be compounded with fiberssuch as glass, graphite or boron fibers to produce molding compounds forhigh strength structural components such as jet engine components. Thepolyimides may also be compounded with friction materials to producemolding compounds for high temperature braking components or withabrasive materials such as diamonds for high speed grinding wheels.

The polyimides may be cast as films useful as wire and cable wraps,motor slot liners or flexible printed circuit substrates. They may beused as coatings on substrates such as aluminum or silicone dioxide.They are also useful to produce high temperature coatings for magneticwire, dip coatings for various electronic components, protectivecoatings over glass, metal and plastic substrates, wear coatings, andphotoresist coatings useful in microelectronic processing.

The polyimides may also be used to produce high temperature adhesivesfor bonding aerospace structures or electrical circuitry, conductiveadhesives when mixed with conductive fillers such as silver or gold formicroelectronic applications, or adhesives for glass, metal or plasticsubstrates.

They may be used as varnish compositions or matrix resins to producecomposites and laminates. The varnish compositions and matrix resins maybe used to impregnate glass or quartz closth, or graphite or boronfibers, for the production of radomes, printed circuit boards,radioactive waste containers, turbine blades, aerospace structuralcomponents or other structural components requiring high temperatureperformance, non-flammability and excellent electrical properties.

The polyamides of this invention may be characterized as havingrecurring groups of the structure: ##STR14## wherein n is the number ofrepeating groups, Y is a divalent organic radical, and Q is a divalentradical as defined in formula (2). Preferably, Q has the structure offormula (3).

The polyamides are prepared by reacting an acid chloride of dicarboxylicacids and a diamine of formula (4). The dicarboxylic acids have thegeneral formula:

    XOOC--Y--COOX                                              (10)

wherein X is hydrogen or halogen, Y is a divalent organic radical,preferably containing an aromatic moiety. Preferably, Y is selected fromthe group consisting of ##STR15## wherein R₅ is a carbon--carbon bond,--0--, --S--, --S0₂ 13 , --CO--, --(CH₂)_(r) --, ##STR16## wherein R₆ isa carbon--carbon bond, --S--, --SO₂ --, --CO--, --CH₂ --, --C₂ H₄ --,##STR17## R₄ is halogen, hydroxy, lower (C₁ -C₆) alkyl, or lower (C₁-C₆) alkoxy, m is 0 to 4, preferably m is 0, r is 1 to 4, s is 1 to 5,and u is 0 to 6, preferably u is 0.

Illustrative of dicarboxylic acids which are suitable for use in thepresent invention are:

phtalic acid;

sophthalic acid;

terephthalic acid;

biphenyl-3,3'-dicarboxylic acid;

biphenyl-4,4'dicarboxylic acid;

bis(3-carbonxyphenyl)methane;

bis(4-carboxyphenyl)methane;

2,2-bis(3-carboxyphenyl)propane;

2,2-bis(4-carboxyphenyl)propane;

naphthalene-2,6-dicarboxylic acid;

bis(3-carboxyphenyl)ether;

bis(4-carboxyphenyl)ether;

bis(3-carboxyphenyl)sulfide;

bis(4-carboxyphenyl)sulfide;

bis(3-carboxyphenyl)sulfone;

bis(4-carboxyphenyl)sulfone;

1,4-cyclohexane dicarboxylic acid;

pentanedioic acid;

hexanedioic acid;

1,4-phenylene diethanoic acid;

2,4-furandicarboxylic acid;

1,4-bis(4-carboxyphenoxy)phenylene;

1,1bis(4-carboxyphenyl)-1-phenyl-2,2,2trifluoroethane;

bis-(4-carboxyphenyl)-methyl phosphane oxide;

4,4'-dicarboxyltetraphenyl silane;

5-tertiary butyl isophthalic acid;

5-bromoisophthalic acid;

5-chloroisophthalic acid;

5-fluoroisophthalic acid;

2,2bis(4-carboxyphenyl)hexafluoropropane;

2,2-bis[4-(4-carboxyphenoxy)phenyl]hexafluoropropane;

1,1-bis[4-(4-carboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane;

and mixtures thereof.

A mixture of at least two dicarboxylic acids may be reacted with adiamine of formula (4) to produce copolyamides.

Preferred polyamides are those prepared from the diamine of formula (5)and the acid chlorides of 2,2-bis(4-carboxyphenyl)hexafluoropropane orthe dicarboxylic acid of the formula: ##STR18##

the synthesis of 2,2-bis(4-carboxyphenyl) hexafluoropropane and itscorresponding diacid chloride is described in U.S. Pat. No. 3,328,352 toKwolek, which is incorporated herein by reference.

The 12F-DCA dicarboxylic acid may be prepared in the following manner:

EXAMPLE 9 Preparation of 4,4'-bis[2-(4-Carboxyphenyl)Hexafluoroisopropyl] Diphenyl Ether

To a clean, driy stainless steel autoclave are charged4,4'-bis(2-hydroxy-hexafluoroisopropyl)diphenyl ether, toluene andhydrogen fluoride in a molar ration of at least 1:2:10 followed bysealing and heating at temperatures of between 100 and 170° C. for 24 to96 hours. The autoclave is then vented at 80° C. and hydrogen fluorideis evaporated. After cooling to room temperature, methylene chloride isadded and the reaction mixture is discharged into water. The organiclayer is separated, washed twice with water, and dried over calciumchloride. The solvent is stripped off and the residue is recrystallizedfrom ethanol yielding 4,4'-bis[2-(4-methylphenyl)hexafluoroisopropyl]diphenyl ether. M.P. 89°-90° C.

4,4'-bis[2-(4-methylphenyl)hexafluoroisopropyl] diphenyl ether isdissolved in cetic acid. A catalyst prepared from Co(OAc)₂ ·4H₂O,Mn(OAc)₂ ·4H₂ O and HBr is acetic acid is then added. The reaction isperformed in a glass pressure vessel by heating the mixture up to 180°C. under oxygen at a pressure of 6.5 bar. After the oxygen uptake hasfinished, the contents of the reaction vessel are discharged into adistillation apparatus and acetic acid is distilled off. The residue iscooled to room temperature and the crystalline product is collected in afunnel filter. After washing several times with acetic acid and water,the 4,4'-bis[2-(4-carboxyphenyl)hexafluoroisopropyl] diphenyl ether isdried in vacuo. M.P. 238°-240° C.

The acid chloride is obtained by adding a few drops of dimethylformamideto a slurry of 4,4'-bis[2-(4-carboxyphenyl)-hexafluoroisopropyl]diphenyl ehter in thionylchloride. The mixture is heated at reflux untilthe evolution of hydrogen chloride stops. The excess thionylchloride isstripped off. Toluene is added to remove the residual thionylchloride bydistillation. The solvent is stripped off and the crude product isrecrystallized from n-hexane. The resulting acid chloride has a meltingpoint of 145°-146° C.

The polyamides of this invention may be prepared by interfacial orsolvent polymerization by reacting the diamine such as 12F-ODA with adiacid chloride at low temperatures (below 100° C). These processes aredescribed in detail in U.S. Pat. No. 2,831,834 to Magat and U.S. Pat.No. 3,063,966 to Kwolek et al., which are incorporated herein byreference.

The following examples illustrate the invention. Unless otherwiseindicated, the inherent viscosity reported in the examples is determinedin dimethyl acetamide at 25° C. at a 0.5 g/dl concentration.

EXAMPLE 10

Into a blender is placed 37.5 ml of water, 37.5 ml of tetrahydrofuran;4.18 g (0.005 moles) of 12F-ODA, 1.06 g of sodium bicarbonate and 0.1 gof benzyltriethyl ammonium chloride. The contents of the blender arestirred rapidly for 5 minutes. A solution of 1.015 g (0.005 moles) ofisophthaloyl chloride in 22.5 ml of tetrahydrofuran is added over aperiod of 3 minutes. An emulsion is formed which is stirred for tenminutes. Thereafter 300 ml of water are added to precipitate thepolymer. This mixture is stirred for additional ten minutes, filtered ina buchner funnel, washed with water, and dried in vacuum overnight at90°-100° C. The yield of the polymer is nearly quantitative. Theinherent viscosity of the polymer is 0.76 dl/g in dimethyl acetamide(0.5% at 25° C.) and it has a glass transition temperature (Tg) of 221°C.

EXAMPLES 11-17

The polyamides shown in Table 2 are prepared in accordance with theprocedure set forth in Example 9 by reacting 0.005 moles of the 12F-ODAdiamine with the following diacid chlorides:

                                      TABLE 2                                     __________________________________________________________________________                            Inherent                                                                            Glass Transit                                   Example                 Viscosity                                                                           Temperature                                     Number                                                                              Diacid(s)         (dl/g)                                                                              (°C.)                                    __________________________________________________________________________    11    2,2-bis(4-chlorocarbonylphenyl)-                                                                0.98  240                                                   hexafluoropropane (0.005 moles)                                         12    4,4'-bis[2-(4-chlorocarbonylphenyl)-                                                            0.27  191                                                   hexafluoroisopropyl]-diphenyl                                                 ether (0.005 moles)                                                     13    oxydiphthaloyl chloride (0.005                                                moles)                                                                  14    1,4-bis(4-chlorocarbonylphenoxy)-                                             benzene (0.005 moles)                                                   15    napthalene-2,6-dicarbonyl chloride                                            (0.005 moles)                                                           16    isophthaloyl chloride (0.0025 moles)                                          and                                                                           terephthaloyl chloride (0.0025 moles)                                   17    terephtaloyl chloride (0.005 moles)                                     __________________________________________________________________________

The polyamides of this invention are especially useful for the shapingof films and fibers. The polyamides are also useful in coatings andcoating compositions. It has been found that these polyamides have lowglass transition temperatures and high solubilities in solvents such asdimethylacetamide, N-methyl pyrrolidone, methyethylketone,tetrahydrofuran, butyrolactone and the like. This combination ofproperties greatly facilitates film casting or dry spinning fromsolutions of such polyamides and permits orientation drawing of the filmor fiber at relatively low temperatures.

The invention also provides new copolyamides, copolyamide-acids/esters,and copolyimides. The copolymers are prepared by reacting dicarboxylicacids or tetracarboxylic acids or derivatives thereof with a mixture ofat least one diamine of formula (4) and at least one diamine having theformula:

    H.sub.2 N--A--NH.sub.2                                     (11)

wherein A is a divalent organic radical, preferably containing anaromatic moiety. Preferably A is selected from the group consisting of##STR19## wherein R₅ is a carbon-carbon bond, --O--, --S--, --SO₂ --,--CO--, --(CH₂)_(r) --, ##STR20## wherein R₆ is a carbon-carbon bond,--S--, --SO₂ --, --CO--, --CH₂ --, --C₂ H₄ --, ##STR21## R₄ is halogen,hydroxy, lower (C₁ -C₆) alkyl, or lower (C₁ -C₆) alkoxy, m is 0 to 4,preferably m is 0, r is 1 to 4, s is 1 to 5, and u is 0 to 6, preferablyu is 0.

Illustrative of diamines which are suitable for use in the presentinvention are:

m-phenylene diamine;

p-phenylene diamine;

1,3-bis(4-aminophenyl) propane;

2,2-bis(4-aminophenyl) propane;

4,4'-diamino-diphenyl methane;

1,2-bis(4-aminophenyl) ethane;

1,1-bis(4-aminophenyl) ethane;

2,2'-diamino-diethyl sulfide;

bis(4-aminophenyl) sulfide;

2,4'-diamino-diphenyl sulfide;

bis(3-aminophenyl) sulfone;

bis(4-aminophenyl) sulfone;

4,4'-diamino-dibenzyl sulfoxide;

bis(4-aminophenyl) ether;

bis(3-aminophenyl) ether;

bis(4-aminophenyl) diethyl silane;

bis(4-aminophenyl) diphenyl silane;

bis(4-aminophenyl) ethyl phosphine oxide;

bis(4-aminophenyl) phenyl phosphine oxide;

bis(4-aminophenyl)-N-phenylamine;

bis(4-aminophenyl)-N-methylamine;

1,2-diamino-naphthalene;

1,4-diamino-naphthalene;

1,5-diamino-naphthalene;

1,6-diamino-naphthalene;

1,7-diamino-naphthalene;

1,8-diamino-naphthalene;

2,3-diamino-naphthalene;

2,6-diamino-naphthalene;

1,4-diamino-2-methyl-naphthalene;

1,5-diamino-2-methyl-naphthalene;

1,3-diamino-2-phenyl-naphthalene;

4,4'-diamino-biphenyl;

3,3'-diamino-biphenyl;

3,3'-dichloro-4,4'-diamino-biphenyl;

3,3'-dimethyl-4,4'-diamino-biphenyl;

3,4'-dimethyl-4,4'-diamino-biphenyl;

3,3'-dimethoxy-4,4'-diamino-biphenyl;

4,4'-bis(4-aminophenoxy)-biphenyl;

2,4-diamino-toluene;

2,5-diamino-toluene;

2,6-diamino-toluene;

3,5-diamino-toluene;

1,3-diamino-2,5-dichloro-benzene;

1,4-diamino-2,5-dichloro-benzene;

1-methoxy-2,4-diamino-benzene;

1,4-diamino-2-methoxy-5-methyl-benzene;

1,4-diamino-2,3,5,6-tetramethyl-benzene;

1,4-bis(2-methyl-4-amino-pentyl)-benzene;

1,4-bis(1,1-dimethyl-5-amino-pentyl)-benzene;

1,4-bis(4-aminophenoxy)-benzene;

o-xylylene diamine;

m-xylylene diamine;

p-xylylene diamine;

3,3'-diamino-benzophenone;

4,4'-diamino-benzophenone;

2,6-diamino-pyridine;

3,5-diamino-pyridine;

1,3-diamino-adamantane;

3,3'-diamino-1,1'-diadamantane;

bis(4-amino-cyclohexyl) methane;

1,5-diamino-pentane;

1,6-diamino-hexane;

1,7-diamino-heptane;

1,8-diamino-octane;

1,9-diamino-nonane;

1,10-diamino-decane;

1,7-diamino-3-methyl-heptane;

1,7-diamino-4,4-dimethyl-heptane;

2,11-diamino-dodecane;

1,3-bis(3-aminopropoxy) ethane;

1,3-diamino-2,2-dimethyl-propane;

1,6-diamino-3-methoxy-hexane;

1,6-diamino-2,5-dimethyl-hexane;

1,7-diamino-2,5-dimethyl-heptane;

1,9-diamino-5-methyl-nonane;

1,4-diamino-cyclohexane;

2,5-diamino-1,3,4-oxadiazole;

N-(3-aminophenyl)-4-aminobenzamide;

4-aminophenyl-3-aminobenzoate;

2,2-bis(4-aminophenyl) hexafluoropropane;

2,2-bis(3-aminophenyl) hexafluoropropane;

2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane;

2,2-bis[4-(2-chloro-4-aminophenoxy)phenyl] hexafluoropropane;

1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane;

1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane;

1,4-bis(3-aminophenyl)buta-1-ene-3-yne;

1,3-bis(3-aminophenyl)hexafluoropropane;

1,5-bis(3-aminophenyl)decafluoropentane; and mixtures thereof.

Preferably, the molar ratio of diamine of formula (4) to diamine offormula (11) is in the range of from about 10:90 to about 99:1, morepreferably of from about 50:50 to about 99:1.

The tetracarboxylic acids and derivatives of formulae (6) and (7) andthe dicarboxylic acids of formula (10) are suitable for the preparationof the copolymers of this invention. The copolyimides and copolyamidesare useful for the utilities discussed above for the polyimides andpolyamides, respectively.

The invention provides new monomers, oligomers, prepolymers and thecorresponding addition polyimides prepared therefrom. The monomers,oligomers and prepolymers are prepared by reacting the diamines offormula (4), or the precursor condensation product of the diamines offormula (4) and the tetracarboxylic acids or derivatives of formulae (6)or (7), with reactive end-capping compounds such as vinyl aromaticanhydrides, nadic acids or derivatives thereof such as anhydrides oracid-esters, maleic anhydrides, aromatic ethynyl amines, orbenzocyclobutene amines.

The monomers, oligomers and prepolymers are useful for adhesivecompositions, coating compositions, laminate varnish compositions, andcomposite matrix resin compositions. They may be reacted by additionpolymerization reactions to provide addition polyimides which are usefulfor coatings, laminates and composites.

One class of addition-type polyimide prepolymers may be characterized ashaving the following structure: ##STR22## wherein n is 0 to 4, R is atetravalent organic radical as defined above, Q is a divalent radical asdefined in formula (2),

R_(a) is ##STR23## R_(b) is hydrogen, halogen preferably fluorine, orlower (C₁ -C₃) alkyl preferably methyl,

R_(c) is ##STR24## Z is --(CH₂)t--, t is 0 to 4, R_(d) is H or R_(c),and R_(e) is H or CH₃.

Preferably, Q has the structure of formula (3), R_(b) is hydrogen, R_(d)is hydrogen, n is 0 or 1, and t is 0 or 1.

Preferably, R_(a) is ##STR25##

Generally speaking, this class of prepolymers may be prepared byreacting dicarboxylic acids, wherein the carboxyl groups are linked toadjacent carbon atoms, or derivatives thereof such as acid-esters oranhydrides, with the diamines of formula (4) or with the condensationproduct of the diamines of formula (4) and the tetracarboxylic acids orderivatives of formulae (6) or (7). The preferred diamine is the 12F-ODAdiamine of formula (5). The preferred end-capping compounds arevinyl-substituted ortho-phthalic acid anhydrides, nadic acid anhydridesand maleic acid anhydrides.

If a dianhydride is to be included in the polymer chain, the diamine maybe condensed first with the dianhydride and then the end-capping agentmay be reacted with this intermediate condensation product.Alternatively, the diamine may be reacted with a mixture of thedianhydride and end-capping agent. The molar ratio of the diamine todianhydride must be sufficient to provide terminal amino groups at theends of the intermediate product for the purpose of reacting the productwith the end-capping agent. Generally, the molar ratios of diamine todianhydride will range from about 2:1 to about 4:3. The preferreddianhydrides are the 6F-DA dianhydride, the 12F-DA dianhydride, the BTDAdianhydride, the ODPA dianhydride, and2,2-bis[4-(3,4-dicarboxyphenoxy)-phenyl]hexafluoropropane dianhydride.

The preparation of bismaleimides prepolymers and the correspondingaddition polyimides is generally shown in U.S. Pat. No. 4,173,700 toGreen et al., which is incorporated herein by reference. Thebismaleimides of the present invention may be characterized as havingthe structure: ##STR26## wherein n is 0 to 4, and R, Q, and R_(b) arethe radicals as defined above. Preferably, Q has the structure offormula (3), R_(b) is hydrogen or fluorine, and n is 0 or 1. Thepreferred end-capping agents are maleic anhydride and difluoromaleicanhydride.

The preparation of bisnadimide prepolymers and the correspondingaddition polyimides is generally shown in U.S. Pat. No. 3,528,950 toHyman, which is incorporated herein by reference. The bisnadimides ofthe present invention may be characterized as having the structure:##STR27## wherein n is 0 to 4, and R, Q, R_(b) and R_(d) are radicals asdefined above. Preferably, Q has the structure of formula (3), R_(b) ishydrogen or methyl, R_(d) is hydrogen, and n is 0 or 1. The preferredend-capping agent is 5-norbornene-2,3-dicarboxylic acid anhydride.

Another method of preparing addition polyimides and polyimide prepregsusing nadic acid compounds is disclosed in U.S. Pat. No. 4,233,258 toSt. Clair, U.S. Pat. No. 4,281,102 to St. Clair et al., and Johnston etal., "A Mechanistic Study of Polyimide Formation from Diester-Diacids,"Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 25, pp.2175-2183 (1987), which are incorporated herein by reference. Accordingto this approach a diamine, a nadic acid-ester, and a tetracarboxylicdiacid-diester are dissolved in a lower alkyl alcohol such as a methanolor ethanol. The nadic acid-ester and tetracarboxylic diacid-diester maybe made by refluxing stoichiometric amounts of the nadic anhydride andtetracarboxylic dianhydride with excess alcohol such as ethanol. Theresulting solution is cooled to room temperature and the diamine is thenadded. The homogeneous mixture may then be used for prepregging ontofibers. The polymerization proceeds through two steps. The first stepinvolves heating to cause imidization (120°-230° C.) to occur resultingin limited chain extension to form low molecular weight norboreneend-capped oligomers. In the second step, the norborene endcaps arecrosslinked by heating to higher temperatures (275°-325° C.). Becausethis final reaction occurs without the release of volatile materials,high quality void-free composites may be fabricated. Typically, thesolvents used in this type of system have been methanol and ethanol.However, it has been found that it is advantageous to use propyleneglycol methyl ether (PGME) as a solvent in this system. By using PGME,certain environmental hazards associated with the handling and disposalof solvents such as methanol and ethanol are avoided. The monomerreactants may be dissolved in up to about a 50 weight percent solutionusing PGME as a solvent.

The following examples are illustrative of prepolymers and additionpolyimides of this invention:

EXAMPLE 18

A four-necked flask fitted with a stirrer and maintained under anitrogen atmosphere is charged with 8.36 g (0.01 moles) of 12F-ODA,2.1573 g (0.022 moles) of maleic anhydride, 90 ml of toluene and 10 mlof DMF. After 1 hour of stirring, 6.6 g of acetic anhydride and 0.5 g ofsodium acetate is added and the mixture is stirred for an additional 1hour. The mixture is then heated to 50° C. for 8 hours. The reactionproduct is then precipitated in an ice-water mixture, filtered, washedseveral times with water and dried overnight in a vacuum oven at 90° C.The resulting product, a bismaleimide, is a yellow powder which turns toclear, transparent flakes upon melting. The melting point is 95° C. (DSCendotherm) and the curing temperature is 310° C. (DSC exotherm peak). Itis soluble in acetone, ethylacetate, NMP, THF, MEK and BLO.

The wide difference between melting endotherm and curing exotherm givesa broad processing window for this class of polymers.

1.0 g of the bismaleimide material is then dissolved in 3.0 ml of NMP.The solution is spread on a glass plate to obtain a uniform film. Theplate is dried first in an air oven at 90° C. for one hour and then at270° C. for one hour to remove the solvent and cure the monomer. Anamber color film is obtained which is slightly brittle. When placed inMEK solvent for an hour at room temperature, no change in filmcharacteristics and no weight loss is observed.

EXAMPLE 19

A 3-neck flask purged with nitrogen and fitted with a condenser,themometer and stirrer is charged with 4.18 g (0.005 moles) of 12F-ODAand 10 g of distilled NMP under a nitrogen atmosphere. The mixture isstirred to obtain a clear solution. 1.693 g (0.01 moles) ofcis-5-norborene-endo-2,3-dicarboxylic acid anhydride (97% pure)(hereinafter "Nadic Anhydride") are added while stirring is continued.13.5 g of NMP are then added and the mixture is stirred overnight atroom temperature. The resulting diamic acid has an inherent viscosity of0.12 dl/g measured at 0.5 g/dl in DMAc at 25° C.

To 20 g of the diamic acid solution, 7.07 g of acetic anhydride and 0.7g of 3-picoline are added. The reaction mixture is stirred at roomtemperature for about six hours. The resulting bisnadimide isprecipitated in methanol, isolated by filtration, washed with freshmethanol, and dried overnight in a vacuum oven at 85° C. It is solublein acetone, DMAc, diglyme, MEK, NMP, THF, chloroform and BLO solvents.

1.0 g of the nadic terminated material is in 3.0 ml of NMP. The solutionis spread over a glass plate to obtain a uniform film. The coated plateis dried in an air oven first at 90° C. for one hour and then at 270° C.for one hour to remove the solvent and cure the monomer. The thuslyobtained film is brittle and not uniform. When placed in MEK solvent foran hour at room temperature, no weight loss is observed.

EXAMPLE 20

A 3-neck flask purged with nitrogen and fitted with a condenser,thermometer, and stirrer is charged with 8.36 g (0.01 moles) of 12F-ODAand 20 g of NMP under a nitrogen atmosphere. The mixture is stirred toobtain a clear solution. 3.81 g (0.005 moles) of 12F-DA are added whilestirring is continued. 1.693 g of Nadic Anhydride is then added alsounder continuous stirring. After charging with 24.45 g of NMP, thereaction mixture is stirred overnight at room temperature. The resultingnadic-terminated polyamic acid has an inherent viscosity of 0.2 dl/gmeasured at 0.5 g/dl in DMAc at 25° C.

To 65 g of the polyamic acid solution, 16.72 g of acetic anhydride and1.672 g of 3-picoline are added. The reaction mixture is stirred at roomtemperature for about six hours. The resulting nadic-terminatedoligomers are precipitated in methanol, isolated by filtration, washedwith fresh methanol, and dried overnight in a vacuum oven at 85° C. Thefinal product is soluble in acetone, DMAc, diglyme, MEK, NMP, THF,chloroform and BLO solvents.

Another class of addition-type polyimide prepolymers may becharacterized as having the following structure: ##STR28## wherein n is1 to 5, preferably n is 1 or 2, R_(g) is ##STR29## R_(h) is H or##STR30## preferably H or --C₆ H₅, R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄--SO₂ --C₆ H₅, preferably H, W is --O--, --S--, --SO₂ --, --CO--, --CH₂--, --C(CH₃)₂ -- or --C(CF₃)₂ --, and t is 0 to 4, preferably t is 0.

This class of prepolymers may be prepared by first reacting the diamineof formula (4) with the tetracarboxylic acids or derivatives of formulae(6) or (7) to produce intermediate compounds having terminal anhydride,diacid, or acid-ester groups. To obtain these intermediates, excessmolar amounts of the dianhydride would be used. Generally, the molarratios of dianhydride to diamine will range from 2:1 to 4:3. Theintermediates are then reacted with end-capping amines. The preferreddianhydrides are the 6F-DA dianhydride, the 12F-DA dianhydride, the BTDAdianhydride, the ODPA dianhydride, and2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride.

The preferred end-capping amines are 4-aminobenzocyclobutene,aminoarylacetylenes, and phenylacetylenearylamines.

The preparation of bisbenzocyclobutene substituted imide oligomers andthe corresponding addition polyimides is generally shown in Tan andArnold, "Benzocyclobutene in Polymer Synthesis I. Homopolymerization ofBisbenzocyclobutene Aromatic Imides to Form High-Temperature ResistantThermosetting Resins, " Journal of Polymer Science, Vol. 25, pp.3159-3172, (1987), which is incorporated herein by reference. Thebenzocyclobutene substituted imide oligomers of the present inventionmay be characterized as having the structure: ##STR31## wherein n is 1to 5, and R and Q are as defined above. Preferably, Q has the structureof formula (3) and n is 1 or 2.

The preparation of acetylene terminated imide oligomers and thecorresponding addition polyimides is generally shown in U.S. Pat. No.4,276,407 to Bilow et al. and PCT Publication No. WO 81/01293, Bilow etal., entitled "Acetylene Terminated Imide Oligomers Having ImprovedSolubilities and Lower Melting Points," which are incorporated herein byreference. The acetylene and phenylacetylene terminated imide oligomersof the present invention may be characterized as having the structure:##STR32## wherein n is 1 to 5, t is 0 to 4, and R, Q, R_(h), and W aredefined as above. Preferably, Q has the structure of formula (3), n is 1or 2, and t is 0.

Suitable end capping amines having terminal acetylene orphenylacetylenyl groups are those having the structure: ##STR33##wherein t is 0 to 4, preferably t is 0, and R_(h) and W are as definedabove. The preferred acetyleneamine is 3-aminophenylacetylene and thepreferred phenylacetylenylamine is 1-amino-3-phenylacetylenyl-benzene.

The following examples are illustrative of imide oligomers and additionpolyimides of this invention:

EXAMPLE 21

A solution of 9.4468 g (0.0113 moles) of 12F-ODA in 50 ml of NMP isadded dropwise to a solution of 9.99 g (0.0225 moles) of 6F-DA in 75 mlof NMP at 50° C. in a three-necked flask equipped with stirrer under anitrogen atmosphere. After heating the reaction contents at 50° C. for30 minutes, a solution of 0.0225 moles of 4-aminobenzocyclobutene in 10ml of NMP is added all at once. 75 ml of toluene is then added and thereaction mixture is refluxed (at about 143° C.) for 12 hours employing aDean-Stark trap to remove the water. The solvent is distilled off usinga mild vacuum. A residue remains which is precipitated using ethanol. Abenzocyclobutene-terminated oligomeric material product is obtainedwhich is washed several times with ethanol and dried overnight in avacuum oven at 90° C.

EXAMPLE 22

A solution of 9.4468 g (0.0113 moles) of 12F-ODA in 50 ml of NMP isadded dropwise to a solution of 9.99 g (0.0225 moles) of 6F-DA in 75 mlof NMP at 50° C. in a three-necked flask equipped with stirrer under anitrogen atmosphere. After heating the reaction contents at 50° C. for30 minutes, a solution of 3.6325 g (0.0225 moles) of3-aminophenylacetylene in 10 ml of NMP is added all at once. 75 ml oftoluene is then added and the reaction mixture is refluxed (at about143° C.) for 12 hours employing a Dean-Stark trap to remove the water.The solvent is distilled off using a mild vacuum. A brown oily residueremains which is precipitated using ethanol. A brown colored product isobtained which is washed several times with ethanol and dried overnightin a vacuum oven at 90° C.

The resulting acetylene-terminated oligomer is a brown powder having amelting point (DSC endotherm) of about 82° C. It is soluble in acetone,ethyl acetate, NMP, THF, MEK and BLO. The curing temperature is 335° C.(DSC exotherm peak) with curing range of about 250°-350° C.

The large difference between the DSC endotherm and the DSC exotherm(82°-335° C.) provides a broad processing window for this class ofpolymers.

The invention provides copolymers prepared by reacting the acetylene orphenylacetylene terminated oligomers of formula (17) with other knownacetylene or phenylacetylene terminated monomers and oligomers. Variousacetylene terminated oligomers are described in, for example, U.S. Pat.No. 4,100,138 to Bilow et al. and U.S. Pat. No. 4,276,407 to Bilow etal., which are incorporated herein by reference. U.S. Pat. No. 4,100,138also describes the copolymerization of acetylene terminated polyimideoligomers with diethynylbenzene. Arylether compounds having terminalphenylethynyl groups are described in U.S. Pat. No. 4,513,131 toReinhardt et al., which is incorporated herein by reference.

The invention further provides compositions of component (A) comprisingknown polymides or copolyimides such as those described in U.S. Pat.Nos. 3,342,774 to Hoegger; 3,356,648 to Rogers; 3,424,718 to Angelo;3,649,601 to Critchley et al.; 3,926,913 to Jones et al.; 3,959,350 toRogers; 4,111,906 to Jones et al.; 4,477,648 to Jones et al.; 4,535,101to Lee et al.; 4,595,548 to St. Clair et al.; 4,603,061 to St. Clair etal.; and 4,612,361 to Peters; which are herein incorporated byreference; or a polyimide of formula (1); or mixtures thereof; andcomponent (B) comprising an addition-type polyimide monomer, oligomer orprepolymer of formulae (12), (13), (14), (15), (16) or (17). In anotheraspect, the invention provides compositions wherein component (A) is apolyimide of formula (1) and wherein component (B) is a knownaddition-type polyimide monomer, oligomer or prepolymer such as thosedescribed in U.S. Pat. Nos. 4,173,700 to Green et al.; 3,528,950 toHyman, 4,233,258 to St. Clair, 4,281,102 to St. Clair et al.; 4,276,407to Bilow et al.; 4,675,370 to Tan et al.; the Tan and Arnold publicationreferred to above; and PCT Publication No. WO 81/01293, Bilow et al.;all of which are incorporated herein by reference. The compositions areuseful for producing films, composites and as matrix resins. When thecompositions are cured, the component (B) material is polymerizedforming interpenetrating networks or semi-interpenetrating networkswhich physically bond the molecules of the component (A) polymer in thenetwork.

Preferably, component (A) is present in the composition in the range offrom about 90 to about 10, more preferably from about 80 to about 20,percent by weight of the total combined weight of components (A) and(B). Preferably, component (B) is present in the composition in therange of from about 10 to about 90, more preferably from about 20 toabout 80, percent by weight of the total combined weight of components(A) and (B).

The following examples are illustrative of the invention:

EXAMPLE 23

A composition is prepared by dissolving 1.0 g of SIXEF-44™ polyimide (apolyimide prepared from 6F-DA dianhydride and 6F-44 diamine), availablefrom Hoechst Celanese Corporation, Somerville, N.J., and 1.0 g of thebismaleimide prepared according to Example 18 in 10.0 ml of NMP. Thesolution is spread over a glass plate to obtain a uniform film. Thecoated plate is dried in an air oven first at 90° C. for one hour andthen at 270° C. for one hour to evaporate the residual solvent and tocause cross-linking of the bismaleimide monomer. A uniform amber colorfilm is obtained which is flexible. When placed in MEK solvent for anhour at room temperature, the film retains 66 percent of its originalweight.

EXAMPLE 24

A composition is prepared by dissolving 1.0 g of SIXEF-44™ polyimide (apolyimide prepared from 6F-DA dianhydride and 6F-44 diamine), availablefrom Hoechst Celanese Corporation, Somerville, N.J., and 1.0 g of thebisnadimide prepared according to Example 19 in 10.0 ml of NMP. Thesolution is spread over a glass plate to obtain a uniform film. Thecoated plate is dried in an air oven first at 90° C. for one hour andthen at 270° C. for one hour to evaporate the residual solvent and tocause cross-linking of the bisnadimide monomer. A uniform amber colorfilm is obtained which is flexible. When placed in MEK solvent for anhour at room temperature, the film retains 61 percent of its originalweight.

EXAMPLE 25

A composition is prepared by dissolving 1.0 g of SIXEF-44™ polyimide (apolyimide prepared from 6F-DA dianhydride and 6F-44 diamine), availablefrom Hoechst Celanese Corporation, Somerville, N.J., and 1.0 g of theacetylene-terminated oligomer prepared according to Example 22 in 10.0ml of NMP. The solution is spread over a glass plate to obtain a uniformfilm. The coated plate is dried in an air oven first at 90° C. for onehour and then at 270° C. for one hour to evaporate the residual solventand to cause cross-linking of the acetylene-terminated oligomer. Auniform film is obtained which is flexible. When placed in boiling MEKsolvent for an hour, no appreciable weight loss is observed.

The present invention also provides bis(amino-imide) compounds havingthe structure: ##STR34## wherein n is 1 to 5,

R is tetravalent organic radical having at least 4 carbon atoms,

Q is ##STR35## and X is hydrogen or halogen.

Preferred are such bis(amino-imide) compounds, wherein Q has thestructure: ##STR36##

The invention also provides epoxy resin compositons. The epoxy resincomposition comprises a polyfunctional epoxy resin and a curing agent.The curing agent may be a diamine of formula (4), a bis(amino-imide)compound of formula (19) or mixtures thereof.

The polyfunctional epoxy resins to which the invention relates arewidely known and described in the literature and need not be redescribedherein.

The ratio by weight of epoxy resin to curing agent is preferably in therange of from about 10:90 to about 90:10, more preferably of from about20:80 to about 80:20.

The compositions of epoxy resins and curing agent are used to impregnatefibers, such as carbon, boron and glass, and may also be filled withparticulate fillers to provide high performance fiber reinforced plasticarticles or filled epoxy resins which are used to fabricate a widevariety of molded articles. The preparation of epoxy resin compositionsand molded articles therefrom is described in the above-referenced U.S.Pat. No. 4,244,857 to Serafini et al. and in D. A. Scola, "Synthesis andCharacterization of Bisimide Amines and Bisimide Amine-Cured EpoxyResins," Polymer Composites, Vol. 4, No. 3, pp. 154-161, (Jul., 1983),which is incorporated herein by reference. The compositions may also beused as adhesives.

The following examples are illustrative of the invention:

EXAMPLE 26

A solution of 10.1 g of 12F-ODA diamine in 10 g of BLO solvent is mixedwith 10 g of a bisphenol A diepoxide (Interez 510) at room temperature.The mixture is cast as a film on two glass plates. One specimen isheated at 90° C. for 3 hours. The resulting film is semihard and notcompletely cured. The other specimen is heated at 110° C. for 3 hours.The resulting film is completely cured and yellow in color.

EXAMPLE 27

A solution of 15.2 g of 12F-ODA diamine in 10 g of BLO solvent is mixedwith 10 g of a bisphenol A diepoxide (Interez 510) at room temperature.The mixture is cast as a film on two glass plates. One specimen isheated at 90° C. for 3 hours. The resulting film is semihard and notcompletely cured. The other specimen is heated at 110° C. for 2 hours.The resulting film is completely cured and yellow in color.

EXAMPLE 28

A solution of 16 g of the bis(amino-imide) compound of formula 19 in 10g of BLO solvent is mixed with 10 g of a bisphenol A diepoxide (Interez510) at room temperature. The mixture is cast on a glass plate andheated at 110° C. for 3 hours resulting in a cured film.

The solvent soluble polyimides and their polyamic acid precursors of theinvention may be used in the preparation of photosensitive compositionsand processed by conventional techniques to provide thermally stablerelief patterns. These photosensitive compositions are useful in manyapplications such as photopolymerizable varnishes or protective layerssuch as passivation overcoat films, planarization layers inmicroelectronic circuits, insulating layers for multi-layered hybridcircuits and as photoresists that provide relief structures of gooddefinition on substrates such as silicon chips, polymeric films andmetal plates. They provide polymeric layers or relief structures thatpossess high thermal and radiation stability, excellent mechanicalproperties and high insulating properties. In other applications such asprinting plates, the tough mechanical properties of thephotopolymerizable compositions of the invention provide a means to makeprinting plates having the capability of giving long printing runs.

In one form, the photosensitive compositions of the invention comprise amixture of a solvent soluble polyimide of the invention, aphotoinitiator and a photopolymerizable compound containing at least twoterminal ethylenically unsaturated groups.

Suitable photopolymerizable material comprises an additionpolymerizable, non-gaseous (boiling temperature above 100° C. at normalatmospheric pressure), ethylenically-unsaturated compound containing atleast two terminal ethylenic groups, and being capable of forming a highmolecular weight polymer by free radical initiated, chain propagatingaddition polymerization. Illustrative examples include tetraethyleneglycol dimethacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol propane triacrylate, polyethyleneglycol (200) or (600) diacrylate, diethylene glycol dimethacrylate,pentaerythritol tetraacrylate, pentaerythritol triacrylate,1,6-hexanediol dimethacrylate, dipentaerythritolmonohydroxypentaacrylate, ethoxylated bisphenol A dimethacrylate,tripropylene glycol diacrylate, tris(2-hydroxyethyl)isocyanurate,trimethylacrylate tris(2-hydroxyethyl)triacrylate, glycerol diacrylate,glycerol triacrylate, hexamethylene diamine, diacrylamide and mixturesthereof.

Suitable photoinitiators useful in the practice of the invention aredisclosed in U.S. Pat. Nos. 4,464,457; 4,465,758 and 4,619,998 which areincorporated herein by reference. A large number of substances can beused in the mixture of the present invention as polymerizationintitiators which can be activated by radiation, particularly actiniclight. Examples are benzoin and its derivatives,trichloromethyl-s-triazines,1,3-bistrichloromethyl-5-(para-biphenyl)triazine-2,4,6;1,3-bistrichloromethyl-5-(para-stilbenyl)triazine-2,4,6; acridinederivatives, for example, 9-phenylacridine, 9-p-methoxyphenylacridine,9-acetylaminoacridine and benz(1)-acridine. Other examples are phenazinederivatives, for example, 9,10-dimethylbenz(a)phenazine and10-methoxybenz(a)-phenazine, quinoxaline derivatives, for example,6,4',4"-trimethoxy-2,3-diphenylquinoxaline and4',4"-dimethoxy-2,3-diphenyl-5-azaquinoxaline. The initiators aregenerally employed in the present invention in an amount of 0.01 to 20,preferably 0.05 to 10 percent by weight, relative to the non-volatilecomponents of the mixture.

The mixture according to the present invention generally contains 20 to90, preferably 30 to 80, percent by weight of solvent soluble polyimideand 80 to 10, preferably 70 to 20, percent by weight of polymerizablecompounds, relative in each case to the total amount of non-volatileethylenically unsaturated monomer and polyimide components.

The mixture can contain, as further conventional components,polymerization inhibitors, oxygen scavengers, hydrogen donors,sensitometric regulators, dyes, pigments, plasticizers and thermallyactivatable crosslinking agents.

It is generally advantageous to substantially isolate the compositionsof the present invention from the influence of atmospheric oxygen duringphotopolymerization. If the composition is used in the form of a thincopying layer, it is recommended that a suitable cover film with a lowpermeability to oxygen be applied to the layer.

Leuco bases of triarylmethane dyes that are suitable for use in thepresent invention include those of Crystal Violet, Victoria Blue BH,Victoria Pure Blue BOH, Methyl Violet, and Acilan Violet S.

Suitable actinic radiation to which the composition according to thepresent invention is sensitive is any electromagnetic radiation whoseenergy is sufficient to initiate polimerization. Visible and ultravioletlight, x-rays and electron radiation are particularly suitable. Laserradiation in the visible and UV range can also be used. Short-wavelengthvisible and near-UV light is preferred.

The photosensitive compositions of the invention may be employed insolution which can be applied to a substrate by any conventional method,such as roller coating, dipping, spraying, whirling and spin coating.They may be prepared into and used as dry films as is taught in U.S.Pat. No. 3,469,982 Celeste which is incorporated herein by reference.

Suitable substrates include silicon, aluminum, glass, polymeric resinboards and films, silicon dioxide, doped silicon dioxide nitride,tantalum, copper, polysilicone ceramics and aluminum/copper mixtures.

Suitable application solvents include N-methyl-pyrrolidone,dimethylformamide, γ-butyrolactone, acetone, diglyme, tetrahydrofuran,propylene glycol methyl ether, propylene glycol methyl ether acetate,and mixtures thereof. The photosensitive composition after exposure maybe developed by any suitable organic solvent, e.g., γ-butyrolactone,toluene, propylene glycol methyl ether/toluene,N-methylpyrrolidone/toluene, acetone/water mixtures etc.

The following examples are illustrative of the photosensitivecompositions of the invention:

EXAMPLE 29

A photosensitive composition is prepared using the solvent solublepolyimide of Example 3:

    ______________________________________                                        Example 3 Polyimide   4.0    grams                                            Pentaerythritol triacrylate                                                                         1.5    grams                                            1,3-bistrichloromethyl-5-                                                                           0.1    grams                                            (p-stilbenyl)triazine-2,4,6                                                   Dye                   0.03   grams                                            Diglyme/BLO (50/50)   16.0   grams                                            ______________________________________                                    

The resulting photosensitive composition is filtered under pressure andis roller coated on an anodized aluminum plate. The coated plate ispre-baked at 90° C. for 3 minutes to obtain a resist film. The film isthen overcoated with a polyvinyl alcohol protective layer (10% in water)and prebaked at 90° C. for 2 minutes. The film is then covered with aphotomask having a striped pattern so that the film and the photomaskare in tight contact. The film is exposed through an Addalux vacuumprinter (2KW, photopolymer lamp/UV broad band radiation) for anirradiation time range of 300 sec. After the irradiation, the coating isfirst rinsed with hot water to remove the polyvinyl alcohol overcoat,then is developed with a mixed solution of 4 volume of BLO and 1 volumeof toluene and rinsed with n-hexane to give a negative image.

Other developers include a mixture of toluene/NMP (9:1) andacetone/water (7:3).

EXAMPLE 30

A photosensitive composition is prepared and processed in accordancewith the procedure of Example 29 using the solvent soluble polyimide ofExample 4:

    ______________________________________                                        Example 4 Polyimide   2.0    grams                                            Pentaerythritol triacrylate                                                                         0.4    grams                                            1,3-bistrichloromethyl-5-                                                                           0.3    grams                                            (p-stilbenyl)triazine-2,4,6                                                   Diglyme/BLO (50/50)   15.0   grams                                            ______________________________________                                    

Similarly, the polyamic acid precursors of the polyimides of theinvention may be substituted for the fully imidized polymers of theforgoing examples 30 and 31. However, after the image is developed, thefilm is converted to a polyimide by baking at 275°-350° C. for 0.5 to 3hours.

The forgoing examples illustrate the use of the polymers of theinvention as negative acting resists. However, they may also be used toproduce positive acting compositions as illustrated by the teachings ofU.S. Pat. No. 4,093,461 which are incorporated herein by reference. Inthese compositions, the polyamic acid precursor is mixed with aphotosensitive orthoquinone or naphthoquinone diazide and processed inthe conventional manner to produce a positive relief structure.

What is claimed is:
 1. A polyimide polymer having groups of thestructure: ##STR37## wherein n is the number of repeating groups,Q is##STR38## X is hydrogen or halogen, R is a tetravalent organic radicalhaving at least 4 carbon atoms.
 2. The polyimide of claim 1, wherein Ris selected from the group consisting of ##STR39## wherein R₂ is acarbon-carbon bond, --O--, --S--, --SO₂ --, --CO--, --(CH₂)_(r) --,##STR40## wherein R₃ is a carbon-carbon bond, --S--, --SO₂ --, --CO--,--CH₂ --, --C₂ H₄ --, ##STR41## R₄ is halogen, hydroxy, lower (C₁ -C₆)alkyl or lower (C₁ -C₆) alkoxy, m is 0 to 2, r is 1 to 4, and s is 1 to5.
 3. The polyimide of claim 1, wherein Q has the structure: ##STR42##4. The polyimide of claim 2, wherein Q has the structure: ##STR43## 5.Polyamide-acid polymeric material having groups of the structure:##STR44## wherein n is the number of repeating groups,Q is ##STR45## Xis hydrogen or halogen, R is a tetravalent organic radical having atleast 4 carbon atoms, and R' is hydrogen or monovalent organic radical.6. The polyamide-acid polymeric material of claim 5, wherein R isselected from the group consisting of ##STR46## wherein R₂ is acarbon-carbon bond, --O--, --S--, --SO₂ --, --CO--, --(CH₂)_(r) --,##STR47## wherein R₃ is a carbon-carbon bond, --S--, --SO₂ --, --CO--,--CH₂ --, --C₂ H₄ --, ##STR48## R₄ is halogen, hydroxy, lower (C₁ -C₆)alkyl or lower (C₁ -C₆) alkoxy, m is 0 to 2, r is 1 to 4, and s is 1 to5.
 7. The polyamide-acid polymeric material of claim 5, wherein Q hasthe structure: ##STR49##
 8. The polyamide-acid polymeric material ofclaim 6, wherein Q has the structure: ##STR50##
 9. Polyamide-acidpolymeric material prepared by reacting a fluorine-containing diaminehaving the formula:

    H.sub.2 N--Q--NH.sub.2

wherein Q is ##STR51## and X is hydrogen or halogen; and at least onedianhydride having the formula: ##STR52## wherein R is a tetravalentorganic radical having at least 4 carbon atoms.
 10. The polyamide-acidpolymeric material of claim 9, wherein the dianhydride is selected fromthe group consisting of:1,2,4,5-benzene tetracarboxylic aciddianhydride; 1,2,3,4-benzene tetracarboxylic acid dianhydride;1,4-bis(2,3-dicarboxyphenoxy) benzene dianhydride;1,3-bis(3,4-dicarboxyphenoxy) benzene dianhydride; 1,2,4,5-naphthalenetetracarboxylic acid dianhydride; 1,2,5,6-naphthalene tetracarboxylicacid dianhydride; 1,4,5,8-naphthalene tetracarboxylic acid dianhydride;2,3,6,7-naphthalene tetracarboxylic acid dianhydride;2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride;2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride;2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride;3,3',4,4'-diphenyl tetracarboxylic acid dianhydride; 2,2',3,3'-diphenyltetracarboxylic acid dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyldianhydride; bis(2,3-dicarboxyphenyl) ether dianhydride;4,4'-bis(2,3-dicarboxyphenoxy) diphenyl ether dianhydride;4,4'-bis(3,4-dicarboxyphenoxy) diphenyl ether dianhydride;bis(3,4-dicarboxyphenyl) sulfide dianhydride;4,4'-bis(2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride;4,4'-bis(3,4-dicarboxphenoxy) diphenyl sulfide dianhydride;bis(3,4-dicarboxyphenyl) sulfone dianhydride; 4.4'-bis(2,3-dicarboxyphenoxy) diphenyl sulfonedianhydride;4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride;3,3',4,4'-benzophenone tetracarboxylic acid dianhydride;2,2',3,3'-benzophenone tetracarboxylic acid dianhydride;2,3,3',4'-benzophenone tetracarboxylic acid dianhydride;4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride;bis(2,3-dicarboxyphenyl)methane dianhydride;bis(3,4-dicarboxyphenyl)methane dianhydride;1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride;1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride;1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride;2,2-bis(2,3-dicarboxyphenyl)propane dianhydride;2,2-bis(3,4-dicarboxyphenyl)propane dianhydride;2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propanedianhydride;2,2-bis[4-(3,4-dicarboxyphenoxy)-3,5-dimethyl)phenyl]propanedianhydride; 1,2,3,4-butane tetracarboxylic acid dianhydride;1,2,3,4-cyclopentane tetracarboxylic acid dianhydride; 2,3,4,5-thiophenetetracarboxylic acid dianhydride; 2,3,4,5-pyrrolidine tetracarboxylicacid dianhydride; 2,3,5,6-pyrazine tetracarboxylic acid dianhydride;1,8,9,10-phenanthrene tetracarboxylic acid dianhydride;3,4,9,10-perylene tetracarboxylic acid dianhydride; 2.2-bis(3,4-dicarboxyphenyl) hexafluoropropanedianhydride;1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;1,1-bis(3,4-dicarboxyphenyl)-1-phenyl-2,2,2-trifluoroethane dianhydride;2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride;and1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethanedianhydride.
 11. The polyamide-acid polymeric material of claim 9,wherein Q has the structure: ##STR53##
 12. The polyamide-acid polymericmaterial of claim 10, wherein Q has the structure: ##STR54## 13.Copolyamide-acid polymeric material prepared by reacting afluorine-containing diamine having the formula:

    H.sub.2 N--Q--NH.sub.2

wherein Q is ##STR55## and X is hydrogen or halogen; and at least onediamine having the formula:

    H.sub.2 N--A--NH.sub.2

wherein A is a divalent organic radical; and at least one aromaticdianhydride having the formula: ##STR56## wherein R is a tetravalentorganic radical having at least 4 carbon atoms.
 14. The copolyamide-acidpolymeric material of claim 13, wherein A is selected from the groupconsisting of ##STR57## wherein R₅ is a carbon-carbon bond, --O--,--S--, --SO₂ --, --CO--, --(CH₂)_(r) --, ##STR58## wherein R₆ is acarbon-carbon bond, --S--, --SO₂ --, --CO--, --CH₂ --, --C₂ H₄ --,##STR59## R₄ is halogen, hydroxy, lower (C₁ -C₆) alkyl, or lower (C₁-C₆) alkoxy, m is 0 to 4, r is 1 to 4, s is 1 to 5, and u is 0 to
 6. 15.The copolyamide-acid polymeric material of claim 13, wherein Q has thestructure: ##STR60##
 16. The copolyamide-acid polymeric material ofclaim 14, wherein Q has the structure: ##STR61##
 17. The copolyimideprepared from the copolyamide-acid polymeric material of claim
 13. 18.The copolyimide prepared from the copolyamide-acid polymeric material ofclaim
 14. 19. The copolyimide prepared from the copolyamide-acidpolymeric material of claim
 15. 20. The copolyimide prepared from thecopolyamide-acid polymeric material of claim
 16. 21. An addition-typepolyimide prepolymer having the structure: ##STR62## wherein n is 0 to4,R is a tetravalent organic radical having at least 4 carbon atoms, Qis ##STR63## X is hydrogen or halogen, R_(a) is ##STR64## R_(b) ishydrogen, halogen or lower (C₁ -C₃)alkyl, R_(c) is ##STR65## R_(d) is Hor R_(c), R_(e) is H or CH₃, Z is --(CH₂)_(t) --, and t is 0 to
 4. 22.The polyimide prepolymer of claim 21, wherein Q has the structure:##STR66##
 23. A bisnadimide prepolymer having the structure: ##STR67##wherein n is 0 to 4,R is a tetravalent organic radical having at least 4carbon atoms, Q is ##STR68## X is hydrogen or halogen.
 24. Thebisnadimide prepolymer of claim 23, wherein Q has the structure:##STR69##
 25. A composition comprising:a nadic acid-ester; a diaminehaving the structure:

    H.sub.2 N--Q--NH.sub.2

wherein Q is ##STR70## and X is hydrogen or halogen; and atetracarboxylic diacid-diester.
 26. The composition of claim 25 whichfurther comprises propylene glycol methyl ether.
 27. The composition ofclaim 25, wherein Q has the structure: ##STR71##
 28. The composition ofclaim 26, wherein Q has the structure: ##STR72##
 29. A bismaleimideprepolymer having the structure: ##STR73## wherein n is 0 to 4,R is atetravalent organic radical having at least 4 carbon atoms, Q is##STR74## X is hydrogen or halogen, and R_(b) is hydrogen, halogen orlower (C₁ -C₂) alkyl.
 30. The bismaleimide prepolymer of claim 29,wherein Q has the structure: ##STR75##
 31. An addition-type polyimideprepolymer having the structure: ##STR76## wherein n is 1 to 5,t is 0 to4, R is a tetravalent organic radical having at least 4 carbon atoms, Qis ##STR77## X is hydrogen or halogen, R_(g) is ##STR78## R_(h) is H or##STR79## R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄ --SO₂ --C₆ H₅, and Y is--O--, --S--, --CO--, --CH₂ --, --C(CH₃)₂ -- or --(CF₃)₂ --.
 32. Thepolyimide prepolymer of claim 31, wherein Q has the structure: ##STR80##33. An acetylene substituted imide oligomer having the structure:##STR81## wherein n is 1 to 5,t is 0 to 4, R is a tetravalent organicradical having at least 4 carbon atoms, Q is ##STR82## X is hydrogen orhalogen, R_(h) is H or ##STR83## R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄--SO₂ --C₆ H₅, and Y is --O--, --S--, --SO₂ --, --CO--, --CH₂ --,--C(CH₃)₂ --or --C(CF₃)₂ --.
 34. The imide oligomer of claim 33, whereinQ has the structure: ##STR84##
 35. A benzocyclobutene substituted imideoligomer having the structure: ##STR85## wherein n is 1 to 5,R is atetravalent organic radical having at least 4 carbon atoms, Q is##STR86## X is hydrogen or halogen.
 36. The imide oligomer of claim 35,as herein Q has the structure: ##STR87##
 37. A photosensitivecomposition comprising a polyimide according to claim 1, aphotopolymerizable compound containing at least two terminalethylenically unsaturated groups and a photoinitiator.
 38. Aphotosensitive composition comprising a polyamide-acid polymericmaterial according to claim 5, a photopolymerizable compound containingat least two terminal ethylenically unsaturated groups and aphotoinitiator.
 39. A photosensitive composition comprising apolyamide-acid polymeric material according to claim 5 and a lightsensitive orthoquinone diazide or ortho naphthoquinone diazide.
 40. Apolyimide polymer prepared from a polyimide prepolymer of claim
 21. 41.A polyimide polymer prepared from a polyimide prepolymer of claim 22.42. A polyimide polymer prepared from a bisnadimide prepolymer of claim23.
 43. A polyimide polymer prepared from a bisnadimide prepolymer ofclaim
 24. 44. A polyimide polymer prepared from a bismaleimideprepolymer of claim
 29. 45. A polyimide polymer prepared from abismaleimide prepolymer of claim
 30. 46. A polyimide polymer preparedfrom a polyimide prepolymer of claim
 31. 47. A polyimide polymerprepared from a polyimide prepolymer of claim
 32. 48. A polyimidepolymer prepared from an imide oligomer of claim
 33. 49. A polyimidepolymer prepared from an imide oligomer of claim
 34. 50. A polyimidepolymer prepared from an imide oligomer of claim
 35. 51. A polyimidepolymer prepared from an imide oligomer of claim
 36. 52. An acticlefabricated from a polyimide polymer of claim
 1. 53. An articlefabricated from a polyamide-acid polymeric material of claim
 5. 54. Anarticle fabricated from a polyamide-acid polyameric material of claim 9.55. An article fabricated from a copolyamide-acid polymeric material ofclaim
 13. 56. An article fabricated from a copolyimide of claim
 17. 57.An article fabricated from a polyimide prepolymer of claim
 21. 58. Anarticle fabricated from a bisnadimide prepolymer of claim
 23. 59. Anarticle fabricated from a bismaleimide prepolymer of claim
 29. 60. Anarticle fabricated from a polyimide prepolymer of claim
 31. 61. Anarticle fabricated from an imide oligomer of claim
 33. 62. An articlefabricated from an imide oligomer of claim
 35. 63. A polymer compositioncomprising a solvent soluble thermoplastic polyimide polymer and athermoset polyimide polymer prepared from an addition-type polyimideprepolymer of claim
 21. 64. A polymer composition comprising a solventsoluble thermoplastic polyimide polymer and a thermoset polyimidepolymer prepared from an addition-type polyimide prepolymer of claim 31.65. A polymer composition comprising a polyimide polymer of claim 1 anda thermoset polyimide polymer prepared from an addition-type polyimidemonomer, oligomer or prepolymer having a reactive endcap group of thestructure: ##STR88## wherein R_(b) is hydrogen, halogen or lower (C₁-C₃)alkyl,R_(c) is ##STR89## R_(d) is H or R_(c), R_(e) is H or CH₃,R_(h) is H or ##STR90## R_(i) is H, --O--C₆ H₅ or --O--C₆ H₄ --SO₂ --C₆H₅, Y is --O--, --S--, --SO₂ --, --CO--, --CH₂ --, --C(CH₃)₂ -- or--(CF₃)₂ --, Z is --(CH₂)_(t) --, and t is 0 to 4.